CN110283328B - Zirconium metal organic framework material used as crystal sponge and preparation method thereof - Google Patents
Zirconium metal organic framework material used as crystal sponge and preparation method thereof Download PDFInfo
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- 239000012621 metal-organic framework Substances 0.000 title claims abstract description 82
- 239000000463 material Substances 0.000 title claims abstract description 71
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 title claims abstract description 59
- 239000013078 crystal Substances 0.000 title claims abstract description 42
- 238000002360 preparation method Methods 0.000 title abstract description 19
- YJTKZCDBKVTVBY-UHFFFAOYSA-N 1,3-Diphenylbenzene Chemical group C1=CC=CC=C1C1=CC=CC(C=2C=CC=CC=2)=C1 YJTKZCDBKVTVBY-UHFFFAOYSA-N 0.000 claims abstract description 16
- 239000000126 substance Substances 0.000 claims abstract description 16
- 239000003960 organic solvent Substances 0.000 claims abstract description 13
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 36
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 36
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 26
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 21
- 239000000243 solution Substances 0.000 claims description 18
- 239000011259 mixed solution Substances 0.000 claims description 15
- -1 3, 5-dibromoaminobenzonitrile Chemical compound 0.000 claims description 14
- 239000000203 mixture Substances 0.000 claims description 14
- LWIHDJKSTIGBAC-UHFFFAOYSA-K tripotassium phosphate Chemical compound [K+].[K+].[K+].[O-]P([O-])([O-])=O LWIHDJKSTIGBAC-UHFFFAOYSA-K 0.000 claims description 14
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 claims description 12
- NFHFRUOZVGFOOS-UHFFFAOYSA-N palladium;triphenylphosphane Chemical compound [Pd].C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 NFHFRUOZVGFOOS-UHFFFAOYSA-N 0.000 claims description 12
- 238000000034 method Methods 0.000 claims description 11
- GLWKJSMSPGFSSM-UHFFFAOYSA-N NC1=C(C=C(C=C1C1=CC=C(C=C1)C(=O)O)C#N)C1=CC=C(C=C1)C(=O)O Chemical compound NC1=C(C=C(C=C1C1=CC=C(C=C1)C(=O)O)C#N)C1=CC=C(C=C1)C(=O)O GLWKJSMSPGFSSM-UHFFFAOYSA-N 0.000 claims description 10
- 239000012074 organic phase Substances 0.000 claims description 10
- 239000002244 precipitate Substances 0.000 claims description 10
- 238000006243 chemical reaction Methods 0.000 claims description 9
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 7
- 229910000160 potassium phosphate Inorganic materials 0.000 claims description 7
- 235000011009 potassium phosphates Nutrition 0.000 claims description 7
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 claims description 6
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 6
- 235000019253 formic acid Nutrition 0.000 claims description 6
- 229910052751 metal Inorganic materials 0.000 claims description 6
- 239000002184 metal Substances 0.000 claims description 6
- DUNKXUFBGCUVQW-UHFFFAOYSA-J zirconium tetrachloride Chemical compound Cl[Zr](Cl)(Cl)Cl DUNKXUFBGCUVQW-UHFFFAOYSA-J 0.000 claims description 6
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 claims description 5
- 239000002253 acid Substances 0.000 claims description 5
- 239000012153 distilled water Substances 0.000 claims description 5
- 238000001035 drying Methods 0.000 claims description 5
- 238000001704 evaporation Methods 0.000 claims description 5
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 5
- 150000003839 salts Chemical class 0.000 claims description 5
- 239000007787 solid Substances 0.000 claims description 5
- 238000005406 washing Methods 0.000 claims description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 4
- 238000001914 filtration Methods 0.000 claims description 4
- 238000010992 reflux Methods 0.000 claims description 4
- 238000003756 stirring Methods 0.000 claims description 3
- 239000012298 atmosphere Substances 0.000 claims description 2
- 238000001816 cooling Methods 0.000 claims description 2
- 239000002274 desiccant Substances 0.000 claims description 2
- 238000002156 mixing Methods 0.000 claims description 2
- 229910052757 nitrogen Inorganic materials 0.000 claims description 2
- 239000012071 phase Substances 0.000 claims description 2
- 239000012266 salt solution Substances 0.000 claims description 2
- 229920006395 saturated elastomer Polymers 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 claims 5
- 150000002148 esters Chemical class 0.000 claims 1
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 abstract description 8
- 239000011630 iodine Substances 0.000 abstract description 8
- 229910052740 iodine Inorganic materials 0.000 abstract description 8
- 238000005516 engineering process Methods 0.000 abstract description 5
- 238000004467 single crystal X-ray diffraction Methods 0.000 abstract description 5
- 238000001179 sorption measurement Methods 0.000 abstract description 4
- 239000011148 porous material Substances 0.000 description 9
- 238000005119 centrifugation Methods 0.000 description 6
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 6
- 239000003446 ligand Substances 0.000 description 6
- 238000012360 testing method Methods 0.000 description 6
- 238000002390 rotary evaporation Methods 0.000 description 5
- 238000012512 characterization method Methods 0.000 description 4
- 238000012986 modification Methods 0.000 description 4
- 239000002904 solvent Substances 0.000 description 4
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 3
- 239000008346 aqueous phase Substances 0.000 description 3
- 230000004048 modification Effects 0.000 description 3
- 239000012299 nitrogen atmosphere Substances 0.000 description 3
- 239000000843 powder Substances 0.000 description 3
- HPALAKNZSZLMCH-UHFFFAOYSA-M sodium;chloride;hydrate Chemical class O.[Na+].[Cl-] HPALAKNZSZLMCH-UHFFFAOYSA-M 0.000 description 3
- 238000005303 weighing Methods 0.000 description 3
- 229910052726 zirconium Inorganic materials 0.000 description 3
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- 229910007746 Zr—O Inorganic materials 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- 238000002447 crystallographic data Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 230000003993 interaction Effects 0.000 description 2
- 229910052943 magnesium sulfate Inorganic materials 0.000 description 2
- CSNNHWWHGAXBCP-UHFFFAOYSA-L magnesium sulphate Substances [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 description 2
- 239000011159 matrix material Substances 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 238000009966 trimming Methods 0.000 description 2
- KZOBYUKSQYFWQH-UHFFFAOYSA-N 4-amino-3,5-diphenylbenzonitrile Chemical compound NC1=C(C=2C=CC=CC=2)C=C(C#N)C=C1C1=CC=CC=C1 KZOBYUKSQYFWQH-UHFFFAOYSA-N 0.000 description 1
- 229910017488 Cu K Inorganic materials 0.000 description 1
- 229910017541 Cu-K Inorganic materials 0.000 description 1
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- 125000004429 atom Chemical group 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000000969 carrier Substances 0.000 description 1
- 239000012295 chemical reaction liquid Substances 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 239000013257 coordination network Substances 0.000 description 1
- 238000012937 correction Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 238000009795 derivation Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000002050 diffraction method Methods 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 229910010272 inorganic material Inorganic materials 0.000 description 1
- 239000011147 inorganic material Substances 0.000 description 1
- XMBWDFGMSWQBCA-UHFFFAOYSA-M iodide Chemical compound [I-] XMBWDFGMSWQBCA-UHFFFAOYSA-M 0.000 description 1
- 229940006461 iodide ion Drugs 0.000 description 1
- 229910052753 mercury Inorganic materials 0.000 description 1
- 230000000877 morphologic effect Effects 0.000 description 1
- 238000012856 packing Methods 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 238000000634 powder X-ray diffraction Methods 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 150000003754 zirconium Chemical class 0.000 description 1
- GBNDTYKAOXLLID-UHFFFAOYSA-N zirconium(4+) ion Chemical compound [Zr+4] GBNDTYKAOXLLID-UHFFFAOYSA-N 0.000 description 1
- 239000013096 zirconium-based metal-organic framework Substances 0.000 description 1
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Abstract
The invention discloses a zirconium metal organic framework material as crystal sponge and a preparation method thereof, belonging to the field of metal organic framework materialsA domain. The chemical formula of the zirconium metal organic framework material is as follows: [ Zr ]6(μ3‑O)4(μ3‑OH)4(OH)2(H2O)2(HCOO)2(L)4]nWherein L is 2' -amino-5 ' -cyano- [1,1':3', 1' -terphenyl]4, 4' -dicarboxylic acid, n is infinity, the integral framework structure is a quadruple interpenetration metal organic framework, the zirconium metal organic framework material belongs to a trigonal system, the space group is R-3c, and the unit cell parameter is
α ═ β ═ 90 °, γ ═ 120 °, unit cell volume
The zirconium metal organic framework material provided by the embodiment of the invention can be used as crystal sponge to realize adsorption of iodine molecules, and the structure of the adsorbed iodine is represented by a single crystal X-ray diffraction technology. The invention widens the application range of the metal organic framework material in the aspect of characterizing guest molecules, in particular to inorganic substances dissolved in non-pure organic solvents.
Description
Technical Field
The invention relates to the field of metal organic framework materials, in particular to a zirconium metal organic framework material used as crystal sponge and a preparation method thereof.
Background
As one of the current popular research materials, metal organic framework Materials (MOFs) have unique application prospects in multiple fields by virtue of their specific framework structures and channel effects. The metal organic framework has highly ordered spatial configuration, stable pore channel structure, excellent adsorption performance and periodically repeated component arrangement, and can fully snoop the structural difference of the metal organic framework on the atomic level by utilizing a single crystal diffraction technology. Research has been conducted to investigate the use of MOFs as carriers for testing guest molecules, a strategy known as crystal sponges. The advantage of this technique is that the relevant configuration and other structural information can be clearly characterized for very small amounts of guest molecules. The method has the advantages that other structural characterization means cannot achieve, and therefore great development is achieved. However, the technology still has its limitations, such as the loaded guest molecules are concentrated on organic molecules, and the solvent system can only select organic solvents, such as cyclohexane. Of course, there are few reports on inorganic materials, such as structural information obtained by modifying a single metal atom after characterization of MOFs using single crystal technology. However, it is very rare to use crystalline sponges for inorganic target molecules, in particular, which can be used in non-aqueous systems. The main reason is that MOFs precursors are very easy to lose crystallinity in the post-modification process under a pure organic environment, and are not suitable for single crystal test.
Disclosure of Invention
In order to solve the above technical problems, the present invention provides a zirconium metal organic framework material as a crystalline sponge, which can be used as a crystalline sponge for inorganic substances, thereby widening the application range of the metal organic framework material, and a method for preparing the same.
The invention constructs a metal organic framework material with higher stability, and prepares the first example of the zirconium metal organic framework material with a quadruple interpenetration structure by a reasonable chemical regulation and control means. The material has high water stability, pore structure and high X-ray diffraction quality. Is very suitable for being used as the crystal sponge aiming at inorganic substances. The series of results not only illustrate the feasibility of crystal engineering for regulating the Zr-MOF material, but also illustrate the decision role of reasonably constructing MOF with a specific configuration for exploiting MOF application.
The technical scheme provided by the invention is as follows:
a zirconium metal organic framework material as a crystal sponge has a chemical formula: [ Zr ]6(μ3-O)4(μ3-OH)4(OH)2(H2O)2(HCOO)2(L)4]nWherein L is 2' -amino-5 ' -cyano- [1,1':3', 1' -terphenyl]-4,4 "-dicarboxylic acid, n being ∞;
the frame structure is a quadruple-interpenetration metal organic framework, belongs to a trigonal system, has a space group of R-3c and a unit cell parameter of
α ═ β ═ 90 °, γ ═ 120 °, unit cell volume
The structure of the zirconium metal organic framework material is as follows:
another object of the present invention is to provide a method for preparing the above zirconium metal organic framework material, the method comprises the following steps:
(1) dissolving 2' -amino-5 ' -cyano- [1,1':3',1 "-terphenyl ] -4, 4" -dimethyl acid in N, N ' -dimethylformamide to prepare a mixed solution;
(2) adding zirconium tetrachloride metal salt into the mixed solution, then adding formic acid, placing the mixture in an oven at the temperature of 115-125 ℃, standing the mixture until the reaction is completed to obtain colorless crystals, and separating the crystals to obtain the zirconium metal organic framework material.
Specifically, in the step (1), the concentration of the 2' -amino-5 ' -cyano- [1,1':3', 1' -terphenyl ] -4,4 ' -dicarboxylic acid in the N, N ' -dimethylformamide is 4 mg/mL-6 mg/mL.
Specifically, the amount of zirconium tetrachloride in the step (2) is 10-15mg calculated by 2.5-3.5 mL of the mixed solution I; the amount of the formic acid is 130-170 mu L.
Specifically, the preparation method of the 2 '-amino-5' -cyano- [1,1':3',1 '-terphenyl ] -4, 4' -dicarboxylic acid in the step (1) is as follows:
(1) under the atmosphere of nitrogen, adding 3, 5-dibromoaminobenzonitrile, 4-methyl phenylboronate and potassium phosphate into 1, 4-dioxane for dissolving, then adding palladium tetrakis (triphenylphosphine) for complete reaction, and cooling to room temperature;
(2) evaporating to remove organic solvent, adding dichloromethane and water, separating organic phase, extracting water phase with dichloromethane for three times, mixing organic phases, washing with saturated salt solution, extracting, and removing water with desiccant to obtain solution A;
(3) the solution a was evaporated to remove the organic solvent, and the solid was dried to obtain 2' -amino-5 ' -cyano- [1,1':3', 1' -terphenyl ] -4,4 "-dicarboxylic acid ester;
(4) reacting 2' -amino-5 ' -cyano- [1,1': dissolving 3', 1' -terphenyl ] -4,4 ' -dicarboxylate in methanol to obtain a solution, adding NaOH, stirring the mixture overnight, then evaporating off the methanol, then adding a large amount of water, acidifying the aqueous residue with hydrochloric acid to a pH of 2-3, filtering the resulting precipitate and washing with distilled water;
(5) the precipitate was dried under vacuum to give 2' -amino-5 ' -cyano- [1,1':3',1 "-terphenyl ] -4, 4" -dicarboxylic acid.
Specifically, the molar ratio of 3, 5-dibromoaminobenzonitrile, methyl 4-phenylboronate, potassium phosphate and tetrakis (triphenylphosphine) palladium in the step (1) is 16.0 to 16.8 mmol: 38.0-40.0 mmol: 93.0-95.0 mmol: 1.1-1.3 mmol.
Specifically, the reflux temperature in the step (1) is 80-100 ℃, and the reflux time is 45-50 hours.
Specifically, the volume ratio of dichloromethane to water in the step (2) is 2: 1.
Specifically, in the step (4), the 2' -amino-5 ' -cyano- [1,1': the ratio of the amount of 3', 1' -terphenyl ] -4,4 "-dicarboxylic acid ester, methanol and NaOH was 10.0-12.0mmol, 100mL, 37.0-38.5 mmol.
Specifically, the drying temperature in the above steps (3) and (5) is 80 ℃.
The synthetic route of 2 '-amino-5' -cyano- [1,1':3',1 '-terphenyl ] -4, 4' -dicarboxylic acid is as follows:
the invention has the beneficial effects that:
(1) the zirconium metal organic frame material provided by the invention has stable Zr6Cluster units, strong Zr-O interaction and stable pore channel structure, particularly the quadruple interpenetration structure of the cluster units and the strong Zr-O interaction can ensure that the material has a close packing mode, and the table of crystalline state materials on X-ray derivation tests is improvedNow, the defect of the crystal sponge as a single crystal diffraction technology is overcome;
(2) the prepared crystal sponge is a polymeric material capable of adsorbing iodine simple substances;
(3) the zirconium metal organic framework material can effectively meet the requirements of the metal organic framework material on new application fields, can effectively improve the performance of material crystal testing, and widens the application range of the metal organic framework material;
(4) the preparation method is simple, and the zirconium metal organic framework material with higher purity can be prepared;
(5) provides a new idea for the preparation of crystal sponge of inorganic substances and exploits the application of MOF with a specific configuration.
Drawings
FIG. 1 is a schematic structural diagram of a zirconium metal organic framework material provided by an embodiment of the present invention;
FIG. 2 is an X-ray single crystal diffraction pattern of a zirconium metal organic framework material provided by an embodiment of the present invention;
FIG. 3 is a powder X-ray diffraction pattern of zirconium metal organic framework material provided in an embodiment of the present invention;
FIG. 4 is a graph of a zirconium metal organic framework material having adsorbed iodine and a deposition pattern;
FIG. 5 is a single crystal X-ray diffraction pattern of a single crystal sample of iodine after adsorption of iodine by a zirconium metal organic framework material provided in an embodiment of the present invention.
Detailed Description
The invention will be further illustrated with reference to specific examples, to which the present invention is not at all restricted.
The embodiment of the invention provides a zirconium metal organic framework material used as a crystal sponge, and the chemical formula of the zirconium metal organic framework material is as follows: [ Zr ]6(μ3-O)4(μ3-OH)4(OH)2(H2O)2(HCOO)2(L)4]nWherein L is 2' -amino-5 ' -cyano- [1,1':3', 1' -terphenyl]-4,4 "-dicarboxylic acid, n ∞, integral frameworkThe structure is a quadruple interpenetration metal organic framework, the zirconium metal organic framework material belongs to a trigonal system, the space group is R-3c, and the unit cell parameter is
α ═ β ═ 90 °, γ ═ 120 °, unit cell volume
The structure of the zirconium metal organic framework material is as follows:
example 1
Preparation of zirconium Metal organic frameworks
The preparation method comprises the following steps:
1. preparation of 2 '-amino-5' -cyano- [1,1':3',1 "-terphenyl ] -4, 4" -dicarboxylic acid:
(1) under a nitrogen atmosphere, 3, 5-dibromoaminobenzonitrile (16.0mmol), methyl 4-phenylboronate (38.0mmol) and potassium phosphate (93.0mmol) were added to a 1, 4-dioxane (500mL) solvent, tetrakis (triphenylphosphine) palladium (1.1mmol) was added, after which the temperature was raised to 80 ℃, refluxed for 45 hours and cooled to room temperature;
(2) after removal of the organic solvent by rotary evaporation, dichloromethane (100mL) and H were added2O (50mL), the organic phase was separated, then the aqueous phase was extracted three times with dichloromethane (60mL), the combined organic phases were washed with saturated brine and extracted with anhydrous MgSO4Drying to obtain a solution A;
(3) the solution a was rotary evaporated to remove the organic solvent, and the solid was dried at 80 ℃ to obtain 2' -amino-5 ' -cyano- [1,1': 4.2g of 3', 1' -terphenyl ] -4,4 "-dicarboxylic acid ester, yield 66.7%;
(4) to a solution of 2' -amino-5 ' -cyano- [1,1': adding NaOH (37.0mmol) to a solution of 3', 1' -terphenyl ] -4,4 "-dicarboxylate (10.0mmol) in MeOH (100mL), stirring the resulting mixture at 80 ℃ overnight, then rotary evaporating off the MeOH, followed by addition of a large amount of water, acidifying the aqueous residue with 2M HCl to a pH of 2-3, filtering the resulting precipitate and washing with distilled water;
(5) the precipitate was dried under vacuum at 80 ℃ to give 2' -amino-5 ' -cyano- [1,1':3',1 "-terphenyl ] -4, 4" -dicarboxylic acid 3.5g, yield 89.7%.
2. Preparation of zirconium Metal organic frameworks
(1) Weighing 14mg of 2' -amino-5 ' -cyano- [1,1':3', 1' -terphenyl ] -4,4 ' -dimethyl acid, dissolving in 2.5mL of N, N ' -dimethylformamide to prepare a mixed solution I, and placing the mixed solution I in a reaction bottle;
(2) directly adding 10mg of zirconium tetrachloride metal salt into the mixed solution I, quickly adding 130 mu L of formic acid, placing the mixture in an oven at 115 ℃, standing the mixture for five days to obtain colorless crystals, and separating the crystals to obtain the zirconium metal organic framework material. And separating the crystal material from the reaction solution by a centrifugation method, wherein the centrifugation rotation speed is 3000r/min, and the centrifugation time is 5 min.
Example 2
Preparation of zirconium Metal organic frameworks
The preparation method comprises the following steps:
1. preparation of 2 '-amino-5' -cyano- [1,1':3',1 "-terphenyl ] -4, 4" -dicarboxylic acid:
(1) under a nitrogen atmosphere, 3, 5-dibromoaminobenzonitrile (16.8mmol), methyl 4-phenylboronate (40.0mmol) and potassium phosphate (95.0mmol) were added to a 1, 4-dioxane (550mL) solvent, tetrakis (triphenylphosphine) palladium (1.3mmol) was added, after which the temperature was raised to 100 ℃, refluxed for 50 hours and cooled to room temperature;
(2) after removal of the organic solvent by rotary evaporation, dichloromethane (100mL) and H were added2O (50mL), the organic phase was separated, then the aqueous phase was extracted three times with dichloromethane (60mL), the combined organic phases were washed with saturated brine and extracted with anhydrous MgSO4Drying to obtain a solution A;
(3) the solution a was rotary evaporated to remove the organic solvent, and the solid was dried at 80 ℃ to obtain 2' -amino-5 ' -cyano- [1,1': 4.8g of 3', 1' -terphenyl ] -4,4 "-dicarboxylic acid ester, yield 65.2%;
(4) to a solution of 2' -amino-5 ' -cyano- [1,1':3', 1' -terphenyl ] -4,4 "-dicarboxylate (12.0mmol) in MeOH (100mL) was added NaOH (38.5mmol), the resulting mixture was stirred at 80 ℃ overnight, then MeOH was removed by rotary evaporation, after which large amount of water was added, the aqueous residue was acidified with 2M HCl to pH 2-3, the resulting precipitate was filtered and washed with distilled water;
(5) the precipitate was dried under vacuum at 80 ℃ to give 2' -amino-5 ' -cyano- [1,1':3',1 "-terphenyl ] -4, 4" -dicarboxylic acid 3.9g, yield 88.9%.
2. Preparation of zirconium Metal organic frameworks
(1) Weighing 18mg of 2' -amino-5 ' -cyano- [1,1':3', 1' -terphenyl ] -4,4 ' -dimethyl acid, dissolving in 3.5mL of N, N ' -dimethylformamide to prepare a mixed solution I, and placing the mixed solution I in a reaction bottle;
(2) directly adding 15mg of zirconium tetrachloride metal salt into the mixed solution I, quickly adding 170 mu L of formic acid, placing the mixture in an oven at 125 ℃, standing the mixture for five days to obtain colorless crystals, and separating the crystals to obtain the zirconium metal organic framework material. And separating the crystal material from the reaction solution by a centrifugation method, wherein the centrifugation rotation speed is 3000r/min, and the centrifugation time is 5 min.
Example 3
Preparation of zirconium Metal organic frameworks
The preparation method comprises the following steps:
1. preparation of 2 '-amino-5' -cyano- [1,1':3',1 "-terphenyl ] -4, 4" -dicarboxylic acid:
(1) under a nitrogen atmosphere, 3, 5-dibromoaminobenzonitrile (16.4mmol), methyl 4-phenylboronate (39.0mmol) and potassium phosphate (94.0mmol) were added to a 1, 4-dioxane (530mL) solvent, tetrakis (triphenylphosphine) palladium (1.2mmol) was added, after which the temperature was raised to 90 ℃, refluxed for 48 hours and cooled to room temperature;
(2) after removal of the organic solvent by rotary evaporation, dichloromethane (100mL) and H were added2O (50mL), the organic phase was separated, the aqueous phase was then extracted three times with dichloromethane (60mL), the combined organic phases were washed with saturated brine and extractedMgSO water4Drying to obtain a solution A;
(3) the solution a was rotary evaporated to remove the organic solvent, and the solid was dried at 80 ℃ to obtain 2' -amino-5 ' -cyano- [1,1': 4.5g of 3', 1' -terphenyl ] -4,4 "-dicarboxylic acid ester, yield 66.2%;
(4) to a solution of 2' -amino-5 ' -cyano- [1,1':3', 1' -terphenyl ] -4,4 "-dicarboxylate (11.0mmol) in MeOH (100mL) was added NaOH (38.0mmol), the resulting mixture was stirred at 80 ℃ overnight, then MeOH was removed by rotary evaporation, after which large amount of water was added, the aqueous residue was acidified with 2M HCl to pH 2-3, the resulting precipitate was filtered and washed with distilled water;
(5) the precipitate was dried under vacuum at 80 ℃ to give 2' -amino-5 ' -cyano- [1,1':3',1 "-terphenyl ] -4, 4" -dicarboxylic acid 3.7g, yield 89.5%.
2. Preparation of zirconium Metal organic frameworks
(1) Weighing 16mg of 2' -amino-5 ' -cyano- [1,1':3', 1' -terphenyl ] -4,4 ' -dimethyl acid, dissolving in 3.0mL of N, N ' -dimethylformamide to prepare a mixed solution I, and placing the mixed solution I in a reaction bottle;
(2) and (2) directly adding 13mg of zirconium tetrachloride metal salt into the mixed solution I, quickly adding 150 mu L of formic acid, placing the mixture in an oven at 120 ℃, standing the mixture for five days to obtain colorless crystals, and separating the crystals to obtain the zirconium metal organic framework material. And separating the crystal material from the reaction liquid by adopting a filtering method.
Application example 1
1. Structural test of zirconium metal organic frame material
1) The zirconium metal organic framework material prepared in example 1 was subjected to structural determination, specifically, the single crystal size of the iron metal organic framework material was measured to be 0.2mm × 0.1mm × 0.1mm, and Cu-K α on Bruker Venture
Measured and the single crystal data was at 100K (empirical absorption of all data)The calibration is completed by software carried by the program), the structure of the zirconium metal organic framework material is shown in figure 1, when in test, the structure analysis and the fine modification are both obtained by the SHELXS-2014 program, and all non-hydrogen atoms adopt the full-matrix least square method (full-matrix-square-defined on F)2) Carrying out structure fine trimming; all non-hydrogen atoms are subjected to anisotropic finishing; the hydrogen atoms on the ligands are generated geometrically symmetrically and the C-H bond length is
The chemical formula of the zirconium metal organic framework material is shown as the following combined measurement results: [ Zr ]6(μ3-O)4(μ3-OH)4(OH)2(H2O)2(HCOO)2(L)4]nWherein L is 2' -amino-5 ' -cyano- [1,1':3', 1' -terphenyl]4, 4' -dicarboxylic acid, n is infinity, the integral framework structure is a quadruple interpenetrating metal organic framework, the zirconium metal organic framework material belongs to a trigonal system, the space group is R-3c, and the unit cell parameter is
α ═ β ═ 90 °, γ ═ 120 °, unit cell volume
The smallest asymmetric unit of the zirconium ion complex comprises four zirconium ions and two ligands. Four zirconium ions form stable Zr through symmetrical growth6The cluster structure is modified with eight ligands at the periphery to form a network configuration with a larger pore structure. Its single crystal X-ray diffraction pattern is shown in FIG. 2.
2) Each zirconium cluster is linked by eight ligands; each ligand is connected with two zirconium clusters to form a PtS configuration coordination network, and a larger pore channel structure is reserved. The pore structure is occupied by other three same grids to form the final quadruple interpenetrating metal organic framework material.
2. Structural characterization and performance test after iodine simple substance adsorption
The test method comprises the following steps:
5-10mg of the zirconium metal organic framework material prepared in the example 1 is weighed and placed in 3-4mL (the volume ratio is 1/30) of a mixed solution of water and acetonitrile containing 10-20mg of elemental iodine.
1) The morphological characterization of the zirconium metal organic framework material is determined, specifically, a Mercury program is adopted to fit a single crystal structure to obtain powder diffraction data, and the powder diffraction data is compared with a powder diffraction pattern actually measured by a zirconium metal organic framework material sample, as shown in fig. 3, after comparison, the peak positions of the zirconium metal organic framework after absorbing iodide ions are basically consistent, so that the purity and the structure of the zirconium metal organic framework material obtained in the embodiment are consistent with those of the experimentally fitted structure, and the sample after absorbing iodide ions also keeps higher stability.
2) The single crystal sample after adsorbing iodide ion was subjected to the same structure determination, specifically, the single crystal size of the iron metal organic framework material was measured to be 0.2mm × 0.1mm × 0.1mm, and Cu-Kalpha was used on Bruker Venture
The structure of the zirconium metal organic framework material is shown in FIG. 1, when the single crystal data is measured at 100K (empirical absorption correction of all data is accomplished by software carried by the program), the structure analysis and fine modification are obtained by the SHELXS-2014 program, and all non-hydrogen atoms are obtained by the full-matrix least squares method (full-matrix-square-based refined on F)2) Carrying out structure fine trimming; all non-hydrogen atoms are subjected to anisotropic finishing; the hydrogen atoms on the ligands are generated geometrically symmetrically and the C-H bond length is
The chemical formula of the zirconium metal organic framework material is shown as the following combined measurement results: { [ Zr)6(μ3-O)4(μ3-OH)4(OH)2(H2O)2(HCOO)2(L)4]6·3(I18)·2(I9)·4(I6) 20(I) wherein L is 2 '-amino-5' -cyano- [1,1':3',1 "-terphenyl]-4,4 "-dicarboxylic acid, nIs infinity, the integral framework structure is a quadruple interpenetration metal organic framework, the zirconium metal organic framework material belongs to a trigonal system, the space group is R-3c, and the unit cell parameter is
α ═ β ═ 90 °, γ ═ 120 °, unit cell volume
The structure of the pore channel after absorbing the iodide ions is the same as the original skeleton structure, and the pore channel is occupied by the iodide ions, as shown in fig. 4. More importantly, the sample after absorbing the iodide ions can still keep higher crystallinity, and the requirement of single crystal X-ray diffraction is met. Its single crystal X-ray diffraction pattern is shown in FIG. 5.
3) The zirconium metal organic framework after absorbing the iodide ions presents three different configurations due to the limited domain effect of the pore channel. Series results show that the zirconium metal organic framework material reported in the patent can still keep high single crystal crystallinity after adsorbing inorganic substances in a non-organic solvent system, and meets the attribute requirement of the metal organic framework material as a crystal sponge aiming at the inorganic substances. Therefore, the patent reports the zirconium metal organic framework material with a quadruple interpenetration structure for the first time, and the extremely high stability of the zirconium metal organic framework material can enable the zirconium metal organic framework material to be applied as crystal sponge aiming at inorganic substances. The achievement not only expands the construction strategy of the zirconium metal organic framework, but also fully explains the importance of the crystallography regulation and control means for constructing the metal organic framework material with specific functions.
The above description is only for the preferred embodiment of the present invention, but the scope of the present invention is not limited thereto, and any modification, equivalent replacement, and improvement made by those skilled in the art within the technical scope of the present invention should be included in the scope of the present invention.
Claims (8)
1. A zirconium metal organic framework material as a crystalline sponge, characterized in that:
the chemical formula of the zirconium metal organic framework material is as follows: [ Zr ]6(μ3-O)4(μ3-OH)4(OH)2(H2O)2(HCOO)2(L)4]nWherein L is 2' -amino-5 ' -cyano- [1,1':3', 1' -terphenyl]-4,4 "-dicarboxylic acid, n being ∞;
the frame structure is a quadruple-interpenetration metal organic framework, belongs to a trigonal system, has a space group of R-3c and a unit cell parameter of
α ═ β ═ 90 °, γ ═ 120 °, unit cell volume
The structure of the zirconium metal organic framework material is as follows:
2. a method for preparing the zirconium metal organic framework material of claim 1, comprising the steps of:
(1) dissolving 2' -amino-5 ' -cyano- [1,1':3', 1' -terphenyl ] -4,4 ' -dimethyl acid in N, N ' -dimethyl formamide to prepare a mixed solution I with the concentration of 4 mg/mL-6 mg/mL;
(2) adding 10-15mg of zirconium tetrachloride metal salt into 2.5-3.5 mL of the mixed solution, then adding 130-170 mu L of formic acid, placing the mixture in an oven at the temperature of 115-125 ℃, standing until the reaction is completed to obtain colorless crystals, and separating out the crystals, namely the zirconium metal organic framework material.
3. The method according to claim 2, wherein the 2 '-amino-5' -cyano- [1,1':3',1 "-terphenyl ] -4, 4" -dicarboxylic acid of step (1) is prepared as follows:
(1) under the atmosphere of nitrogen, adding 3, 5-dibromoaminobenzonitrile, 4-methyl phenylboronate and potassium phosphate into 1, 4-dioxane for dissolving, then adding palladium tetrakis (triphenylphosphine) for complete reaction, and cooling to room temperature;
(2) evaporating to remove organic solvent, adding dichloromethane and water, separating organic phase, extracting water phase with dichloromethane for three times, mixing organic phases, washing with saturated salt solution, extracting, and removing water with desiccant to obtain solution A;
(3) the solution a was evaporated to remove the organic solvent, and the solid was dried to obtain 2' -amino-5 ' -cyano- [1,1':3', 1' -terphenyl ] -4,4 "-dicarboxylic acid ester;
(4) reacting 2' -amino-5 ' -cyano- [1,1': dissolving 3', 1' -terphenyl ] -4,4 ' -dicarboxylate in methanol to obtain a solution, adding NaOH, stirring the obtained mixture overnight, then evaporating to remove methanol, then adding a large amount of water, acidifying the aqueous residue with hydrochloric acid to a pH of 2-3, filtering the obtained precipitate and washing with distilled water;
(5) the precipitate was dried under vacuum to give 2' -amino-5 ' -cyano- [1,1':3',1 "-terphenyl ] -4, 4" -dicarboxylic acid.
4. The production method according to claim 3, characterized in that: the mol ratio of the 3, 5-dibromoaminobenzonitrile to the methyl 4-phenylboronate to the potassium phosphate to the tetrakis (triphenylphosphine) palladium in the step (1) is 16.0-16.8 mmol: 38.0-40.0 mmol: 93.0-95.0 mmol: 1.1-1.3 mmol.
5. The production method according to claim 3, characterized in that: the reflux temperature in the step (1) is 80-100 ℃, and the reflux time is 45-50 hours.
6. The production method according to claim 3, characterized in that: the volume ratio of the dichloromethane to the water in the step (2) is 2: 1.
7. The production method according to claim 3, characterized in that: the ratio of 2' -amino-5 ' -cyano- [1,1': the dosage ratio of the 3', 1' -terphenyl ] -4,4 ' -dicarboxylic ester, the methanol and the NaOH is 10.0-12.0mmol, 100mL and 37.0-38.5 mmol.
8. The production method according to claim 3, characterized in that: the drying temperature in the steps (3) and (5) is 80 ℃.
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